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SECTION 1. CHEMICAL IDENTIFICATION

CHEMINFO Record Number: 599
CCOHS Chemical Name: Ethyl formate

Synonyms:
Ethyl formic ester
Ethyl methanoate
Formic acid, ethyl ester
Formic ether

Chemical Name French: Formate d'éthyle
Chemical Name Spanish: Formiato de etilo
CAS Registry Number: 109-94-4
UN/NA Number(s): 1190
RTECS Number(s): LQ8400000
EU EINECS/ELINCS Number: 203-721-0
Chemical Family: Aliphatic carboxylic acid ester / saturated aliphatic carboxylic acid ester / saturated aliphatic monocarboxylic acid ester / alkyl alkanoate / ethyl ester / formate
Molecular Formula: C3-H6-O2
Structural Formula: H-C(=O)-O-CH2-CH3

SECTION 2. DESCRIPTION

Appearance and Odour:
Colourless liquid with a fruity or aromatic odour.(10,11,12)

Odour Threshold:
18-20 ppm (54-61 mg/m3) (recognition) (11,12) However, these reported values are not considered reliable.(12)

Warning Properties:
NOT RELIABLE - reported odour threshold values are not reliable and are only one-fifth of the TLV and therefore, may not provide adequate warning.

Composition/Purity:
May contain small amounts of ethanol.

Uses and Occurrences:
Used in the lacquer industry; as a solvent for cellulose acetate, nitrocellulose and oils and greases; as a fungicide and larvicide for tobacco, cereals and dried fruit; as a synthetic flavour (especially in lemonade and rum); in the manufacture of artificial rum and arrac; in fragrances; as an intermediate in organic synthesis; substitute for acetone in the production of Estrazolam (an anticonvulsant drug); in the manufacture of safety glass; and in synthetic resins.(10)
It occurs naturally in orange juice, honey, apples and pears, and distilled liquors, such as rum.(2,10)


SECTION 3. HAZARDS IDENTIFICATION

EMERGENCY OVERVIEW:
Colourless liquid with a fruity or aromatic odour. EXTREMELY FLAMMABLE LIQUID AND VAPOUR. Vapour is heavier than air and may spread long distances. Distant ignition and flashback are possible. The vapour is irritating to the nose and throat. May cause lung injury--effects may be delayed. Central nervous system depressant. High vapour concentrations may cause headache, nausea, dizziness, incoordination and confusion. Very high concentrations may cause unconsciousness and death. Causes eye irritation.



POTENTIAL HEALTH EFFECTS

Effects of Short-Term (Acute) Exposure

Inhalation:
Ethyl formate easily forms high vapour concentrations at room temperature posing a significant inhalation hazard. At relatively low airborne concentrations (330 ppm), the vapour can irritate the nose and throat, based on human and animal information.(1,2) Higher concentrations can cause central nervous system (CNS) depression, based on animal information. Symptoms may include incoordination, fatigue, nausea, headache, and, if the exposure is high enough unconsciousness and death. It has been reported that 10,000 ppm is anesthetic and fatal.(1)
Severe exposures may cause a potentially fatal accumulation of fluid in the lungs (pulmonary edema), based on animal information. Typically, the symptoms of pulmonary edema, such as shortness of breath, may not appear until a few hours after exposure.
Irritation of the nose (described as strong and persistent) was experienced by volunteers exposed to 330 ppm for an unspecified duration.(1,2)

Skin Contact:
The liquid is not expected to be irritating, based on human and animal information. No irritation was experienced by volunteers following applications of undiluted ethyl formate for 5 hours.(2) Similarly, no irritation was experienced in volunteers following application of 4% ethyl formate in petrolatum (for 48 hours), using a patch that minimized evaporation.(2)
Ethyl formate is slightly absorbed through the skin (3), but this route of exposure is not expected to produce significant toxic effects, based on animal information.

Eye Contact:
Ethyl formate liquid can probably cause moderate to severe irritation, based on animal information. It reacts slowly with moisture to form corrosive formic acid.(3) There is no human information available for the liquid.
The vapour has caused eye irritation in humans. Irritation was experienced by volunteers exposed to vapour concentrations of 330 ppm (duration unspecified). The effect subsided only after several hours.(2,4)

Ingestion:
Ethyl formate may cause irritation of the mouth and throat. It can be absorbed into the bloodstream following ingestion.(3) This may cause drowsiness, incoordination, shortness of breath and other symptoms of depression of the central nervous system; ingestion of larger amounts may lead to unconsciousness. There is no human or animal information, but these effects have been observed following inhalation. Ingestion is not a typical route of occupational exposure.

Effects of Long-Term (Chronic) Exposure

Skin:
Repeated or prolonged contact with solvents in general may cause dermatitis (red, itchy, dry skin).

Skin Sensitization:
No sensitization reactions were observed in 23 volunteers following application of 4% ethyl formate in petrolatum.(2)

Carcinogenicity:

There is no human information available. Cancer was not observed in one animal study.

The International Agency for Research on Cancer (IARC) has not evaluated the carcinogenicity of this chemical.

The American Conference of Governmental Industrial Hygienists (ACGIH) has not assigned a carcinogenicity designation to this chemical.

The US National Toxicology Program (NTP) has not listed this chemical in its report on carcinogens.

Teratogenicity and Embryotoxicity:
There is no human or animal information available.

Reproductive Toxicity:
There is no human or animal information available.

Mutagenicity:
There is no information available.

Toxicologically Synergistic Materials:
There is no information available

Potential for Accumulation:
Ethyl formate or its metabolites probably do not accumulate in the body. It reacts with water to form formic acid and ethanol, which are readily exhaled, excreted, or metabolized then excreted.


SECTION 4. FIRST AID MEASURES

Inhalation:
If victim is unconscious or does not respond, take proper precautions to ensure your own safety before attempting rescue, e.g. wear appropriate protective equipment, use the "buddy" system. Remove source of contamination or move victim to fresh air. If breathing has stopped, trained personnel should begin artificial respiration or, if the heart has stopped, cardiopulmonary resuscitation (CPR) immediately. If breathing is difficult, oxygen may be beneficial if administered by a person trained in its use, preferably on a doctor's advice. Quickly transport victim to an emergency care facility or obtain medical attention immediately.

Skin Contact:
As quickly as possible, flush contaminated area with lukewarm, gently flowing water for at least 5 minutes, or until the chemical is removed. If irritation persists, obtain medical attention immediately. Completely decontaminate clothing, shoes and leather goods before re-use or discard.

Eye Contact:
Immediately flush the contaminated eye(s) with lukewarm, gently flowing water for 20 minutes, or until the chemical is removed, while holding the eyelid(s) open. Take care not to rinse contaminated water into the non-affected eye. Obtain medical attention immediately.

Ingestion:
NEVER give anything by mouth if victim is rapidly losing consciousness, or is unconscious or convulsing. Have victim rinse mouth thoroughly with water. DO NOT INDUCE VOMITING. Have victim drink 240 to 300 mL (8 to 10 ozs) of water. If vomiting occurs naturally, have victim rinse mouth and repeat administration of water. Obtain medical attention immediately.

First Aid Comments:
Provide general supportive measures (comfort, warmth, rest).
Consult a doctor and/or the nearest Poison Control Centre for all exposures except minor instances of inhalation or skin contact.
Some recommendations in the above sections may be considered medical acts in some jurisdictions. These recommendations should be reviewed with a doctor and appropriate delegation of authority obtained, as required.
All first aid procedures should be periodically reviewed by a doctor familiar with the material and its conditions of use in the workplace.



SECTION 5. FIRE FIGHTING MEASURES

Flash Point:
-20 deg C (-4 deg F) (closed cup) (14)

Lower Flammable (Explosive) Limit (LFL/LEL):
2.8% (14)

Upper Flammable (Explosive) Limit (UFL/UEL):
16% (14)

Autoignition (Ignition) Temperature:
455 deg C (851 deg F) (14)

Sensitivity to Mechanical Impact:
Probably not sensitive. Stable material.

Sensitivity to Static Charge:
Will not accumulate static charge, since it has a high electrical conductivity (1.45 X 10(5) pS/m).(15) Vapours in the flammable range may be ignited by a static discharge of sufficient energy.

Combustion and Thermal Decomposition Products:
Formaldehyde may be formed.

Fire Hazard Summary:
Extremely flammable liquid. Material will readily ignite at room temperature. Vapour is heavier than air and may travel a considerable distance to a source of ignition and flash back to a leak or open container. During a fire, irritating/toxic gases may be generated. Can accumulate in confined spaces, resulting in a toxicity and flammability hazard. Closed containers may rupture violently when heated.

Extinguishing Media:
Carbon dioxide, dry chemical powder, alcohol foam or polymer foam. Water may be ineffective because it will not cool ethyl formate below its flash point. Fire fighting foams are the extinguishing agent of choice for most flammable liquid fires.(16)

Fire Fighting Instructions:
Evacuate area and fight fire from a safe distance or protected location. Approach fire from upwind to avoid toxic decomposition products.
Stop leak before attempting to stop the fire. If the leak cannot be stopped, and if there is no risk to the surrounding area, let the fire burn itself out. If the flames are extinguished without stopping the leak, vapours could form explosive mixtures with air and reignite.
Water can extinguish the fire if used under favourable conditions and when hose streams are applied by experienced firefighters trained in fighting all types of flammable liquid fires. If possible, isolate materials not yet involved in the fire, and move containers from fire area if this can be done without risk, and protect personnel. Otherwise, fire-exposed containers or tanks should be cooled by application of hose streams and this should begin as soon as possible (within the first several minutes) and should concentrate on any unwetted portions of the container. If this is not possible, use unmanned monitor nozzles and immediately evacuate the area.
If a leak or spill has not ignited, use water spray in large quantities to disperse the vapours and to protect personnel attempting to stop a leak. Water spray can be used to dilute spills to nonflammable mixtures and flush spills away from ignition sources. Solid streams of water may be ineffective and spread material.
For a massive fire in a large area, use unmanned hose holder or monitor nozzles; if this is not possible withdraw from fire area and allow fire to burn. Stay away from ends of tanks, but be aware that flying material from ruptured tanks may travel in any direction. Withdraw immediately in case of rising sound from venting safety device or any discolouration of tank due to fire.
Although ethyl formate is only slightly hazardous to health, it may form hazardous decomposition products. Do not enter without wearing specialized protective equipment suitable for the situation. Firefighter's normal protective equipment (Bunker Gear) may not provide adequate protection. Chemical resistant clothing (e.g. chemical splash suit) and positive pressure self-contained breathing apparatus (MSHA/NIOSH approved or equivalent) may be necessary.



NATIONAL FIRE PROTECTION ASSOCIATION (NFPA) HAZARD IDENTIFICATION

NFPA - Health: 2 - Intense or continued (but not chronic) exposure could cause temporary incapacitation or possible residual injury.
NFPA - Flammability: 3 - Liquids and solids that can be ignited under almost all ambient temperature conditions.
NFPA - Instability: 0 - Normally stable, even under fire conditions, and not reactive with water.

SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES

Molecular Weight: 74.08

Conversion Factor:
1 ppm = 3.024 mg/m3; 1 mg/m3 = 0.331 ppm at 25 deg C (calculated)

Physical State: Liquid
Melting Point: -80 deg C (-112 deg F) (14,16)
Boiling Point: 54-55 deg C (129-131 deg F) (17)
Relative Density (Specific Gravity): 0.917 at 20 deg C (water = 1) (16,18)
Solubility in Water: Soluble (10.5 g/100 mL at 20 deg C; 11.8 g/100 mL at 25 deg C).(11)
Solubility in Other Liquids: Soluble in all proportions in ethanol and diethyl ether; very soluble in acetone and benzene.(10,18)
Coefficient of Oil/Water Distribution (Partition Coefficient): Log P(oct) = 0.23 (10)
pH Value: Pure ethyl formate is probably neutral. It decomposes slowly in water, releasing formic acid.
Vapour Density: 2.55 (air = 1) (11)
Vapour Pressure: 25.6 kPa (192 mm Hg) at 20 deg C; 40 kPa (300 mm Hg) at 30 deg C (11)
Saturation Vapour Concentration: 252700 ppm (25.27%) at 20 deg C; 394800 ppm (39.48%) at 30 deg C (calculated)
Evaporation Rate: Not available
Critical Temperature: 235.25 deg C (455.45 deg F) (cited as 508.4 deg K) (18)

Other Physical Properties:
VISCOSITY-DYNAMIC: 0.41 mPa.s (0.41 centipoises) at 20 deg C (17); 0.358 mPa.s (0.358 centipoises) at 30 deg C (18)
VISCOSITY-KINEMATIC: 0.447 mm2/s (0.447 centistokes) at 20 deg C (calculated)
SURFACE TENSION: 23.87 mN/m (23.87 dynes/cm) at 20 deg C; 23.18 mN/m (23.18 dynes/cm) at 25 deg C (calculated) (18)
CRITICAL PRESSURE: 4742 kPa (46.8 atm) (18)


SECTION 10. STABILITY AND REACTIVITY

Stability:
Normally stable. Can gradually decompose (hydrolyze) in water to form formic acid and ethanol.(10,15)

Hazardous Polymerization:
Does not occur

Incompatibility - Materials to Avoid:

NOTE: Chemical reactions that could result in a hazardous situation (e.g. generation of flammable or toxic chemicals, fire or detonation) are listed here. Many of these reactions can be done safely if specific control measures (e.g. cooling of the reaction) are in place. Although not intended to be complete, an overview of important reactions involving common chemicals is provided to assist in the development of safe work practices.


OXIDIZING MATERIALS (e.g. chlorine, fluorine, perchlorates or peroxides) - reaction can be violent. Increased risk of fire and explosion.(15,16,19)
NITRATES - May explode.(19)
STRONG ACIDS (e.g. sulfuric acid, oleum, and chlorosulfonic acid) or STRONG BASES (sodium or potassium hydroxide or sodium methoxide) - extremely unstable and decomposition (hydrolysis) can occur, releasing heat. The reaction may be vigorous or violent.(16,19,20)

Hazardous Decomposition Products:
Ethanol and formic acid

Conditions to Avoid:
Flames, sparks, electrostatic discharge, heat and other ignition sources, moisture.

Corrosivity to Metals:
Anhydrous ethyl formate is not corrosive to iron, steel, stainless steel, aluminum, and copper and nickel and their alloys,.(21) In the presence of water or moisture, ethyl formate may decompose slowly to formic acid, which is corrosive to iron, steel, some stainless steels, copper and its alloys, and lead. Hot ethyl formate (above 93 deg C) may corrode cast iron, steel and aluminum.(21)

Stability and Reactivity Comments:
No specific information is available. A closely related ester, methyl formate, attacks some plastics, rubber and coatings.


SECTION 11. TOXICOLOGICAL INFORMATION

LD50 (oral, rat): 1850 mg/kg (2); 4290 mg/kg (5)
LD50 (oral, guinea pig): 1110 mg/kg (2)
LD50 (oral, rabbit): 2100 mg/kg (cited as 28 mmol/kg) (6)

LD50 (dermal, rabbit): greater than 5000 mg/kg (2); greater than 18000 mg/kg (cited as 20 mL/kg) (5)

Eye Irritation:

Application of 0.1 mL of undiluted ethyl formate caused severe injury in rabbits (graded 4/10; scored over 5 where 5 is severe injury).(5) Moderate irritation was observed in rabbits in a similar study.(7, unconfirmed) Irritation was observed in mice and cats following exposure to 5000 ppm vapour for 20 minutes.(2)

Skin Irritation:

Application of 0.01 mL ethyl formate caused no irritation in rabbits (graded 1/10).(5) In another test, undiluted ethyl formate was not irritating to rabbits when applied to intact or abraded skin, under a covering, for 24 hours.(2)

Effects of Short-Term (Acute) Exposure:

Inhalation:
Irritation of the respiratory tract was observed in mice and cats exposed to 5000 ppm for 20 minutes in one study and in cats exposed to 10560 ppm for 20 minutes in another study.(2,8) Central nervous system (CNS) depression was observed after 80 minutes in cats exposed to 10560 ppm. Deaths occurred due to accumulation of fluid in the lungs (pulmonary edema) after 90 minutes.(8) Death of 5/6 rats occurred following exposure to 8000 ppm for 4 hours. No deaths occurred following exposure to close to the saturated vapour concentration (approximately 252000 ppm) for 5 minutes.(5)

Effects of Long-Term (Chronic) Exposure:

Ingestion:
A drastic (50%) reduction in body weight and evidence of harmful effects on the kidney were observed in rabbits fed 6.8 mg daily (approximately 3.4 mg/kg/day) for 3 months.(2, unconfirmed) In contrast, another study reported no observable harmful effects in rats fed up to 1% (approximately 500 mg/kg/day) ethyl formate in the diet for 17 weeks.(2)

Carcinogenicity:
Cancer was not observed in mice following application of 0.3 mL ethyl formate to the skin daily for 10 weeks, followed by treatments with a tumour promoter.(9)


SECTION 16. OTHER INFORMATION

Selected Bibliography:
(1) Smyth, H.F., Jr. Hygienic standards for daily inhalation. American Industrial Hygiene Association Quarterly. Vol. 17 (June 1956). p. 129-185
(2) Opdyke, D.L.J. Monographs on fragrance raw materials: ethyl formate. Food and Cosmetics Toxicology. Vol. 16, no. 1 (Feb. 1978). p. 737-739
(3) Bisesi, M.S. Esters. In: Patty's industrial hygiene and toxicology. 4th ed. Vol. 2. Toxicology. Part D. Edited by G.D. Clayton, et al. John Wiley and Sons, Inc., 1994. p. 2967-3118
(4) Grant, W.M., et al. Toxicology of the eye. 4th ed. Charles C. Thomas, 1993. p. 673
(5) Smyth, H.F., Jr., et al. Range-finding toxicity data: list V. A.M.A. Archives of Industrial Hygiene and Occupational Medicine. Vol. 10 (1954). p. 61-68
(6) Munch, J.C. Aliphatic alcohols and alkyl esters: narcotic and lethal potencies to tadpoles and to rabbits. Industrial Medicine. Vol. 41, no. 4 (Apr. 1972). p. 31-33
(7) RTECS record for formic acid, ethyl ester. Last updated: 1997/12
(8) von Oettingen, W.F., et al. The aliphatic acids and their esters: toxicity and potential dangers. A.M.A. Archives of Industrial Health. Vol. 20 (Dec. 1959). p. 81/517-95/531
(9) Roe, F.J.C., et al. Further studies on incomplete carcinogenesis: triethylene melamine (T.E.M.), 1,2-benzanthracene and beta-propiolactone, as initiators of skin tumour formation in the mouse. The British Journal of Cancer. Vol. 9 (1955). p. 177-203
(10) HSDB record for ethyl formate. Last revision date: 97/01/24
(11) Verschueren, K. Handbook of environmental data on organic chemicals. 3rd ed. Van Nostrand Reinhold, 1996. p. 980
(12) Odor thresholds for chemicals with established occupational health standards. American Industrial Hygiene Association, 1989. p. 19, 59
(13) Fire protection guide to hazardous materials. 13th ed. Edited by A.B. Spencer, et al. National Fire Protection Association, 2002. NFPA 325
(14) Tau, K.D., et al. Esters, organic. In: Kirk-Othmer encyclopedia of chemical technology. 4th ed. Vol. 9 . John Wiley and Sons, 1994. p. 781-812
(15) Chemical safety sheets: working safely with hazardous chemicals. Kluwer Academic Publishers, 1991. p. 413
(16) The Sigma-Aldrich library of chemical safety data. Ed. II. Vol. 1. Sigma-Aldrich Corporation, 1988
(17) Stoye, D., et al. Solvents. In: Ullman's encyclopedia of industrial chemistry. 5th revised ed. Vol. A 24. VCH Verlagsgesellschaft, 1993. p. 448-453, 476-484
(18) Dean, J.A. Lange's handbook of chemistry. 14th ed. McGraw-Hill, Inc., 1992. p. 1.206, 5.107, 6.139
(19) Pohanish, R.P., et al. Rapid guide to chemical incompatibilities. Van Nostrand Reinhold, 1997. p. 358
(20) Urben, P.G., ed. Bretherick's handbook of reactive chemical hazards. 5th ed. Vol. 1. Butterworth-Heinemann, Ltd., 1995. p. 446
(21) Corrosion data survey: metals section. 6th ed. National Association of Corrosion Engineers, 1985. p. 56-13 to 57-13
(22) NIOSH pocket guide to chemical hazards. National Institute for Occupational Safety and Health, June, 1994. p. 140-141
(23) Forsberg, K., et al. Quick selection guide to chemical protective clothing. 2nd ed. Van Nostrand Reinhold, 1993. p. 54
(24) European Communities. Commission Directive 98/98/EC. Dec. 15, 1998

Information on chemicals reviewed in the CHEMINFO database is drawn from a number of publicly available sources. A list of general references used to compile CHEMINFO records is available in the database Help.


Review/Preparation Date: 1999-02-01

Revision Indicators:
Bibliography 2000-04-01
EU Class 2000-04-01
EU Risk 2000-04-01
EU Safety 2000-04-01
Emergency overview 2000-08-01
Acute exposure (ingestion) 2000-08-01
First aid (ingestion) 2000-08-01
Bibliography 2003-04-18
PEL transitional comments 2003-12-19
PEL-TWA final 2003-12-19



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